CN1615177B - Method of making molecular sieve catalyst - Google Patents

Method of making molecular sieve catalyst Download PDF

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Publication number
CN1615177B
CN1615177B CN028272455A CN02827245A CN1615177B CN 1615177 B CN1615177 B CN 1615177B CN 028272455 A CN028272455 A CN 028272455A CN 02827245 A CN02827245 A CN 02827245A CN 1615177 B CN1615177 B CN 1615177B
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molecular sieve
particle
sieve catalyst
dry
catalyst
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CN1615177A (en
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常云峯
S·N·瓦根
J·W·斯普林科
F·A·希普雷
K·R·克莱姆
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ExxonMobil Chemical Patents Inc
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Exxon Chemical Patents Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/83—Aluminophosphates [APO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
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  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed is a method for making molecular sieve catalyst particles. Dried molecular sieve catalyst particles are used to make the catalyst. The dried molecular sieve catalyst particles are put into an aqueous solution and stirred to make a slurry. The slurry is dried to make the molecular sieve catalyst particles. Optionally, the dried molecular sieve catalyst particles made from the slurry are calcined.

Description

The preparation method of molecular sieve catalyst
Invention field
The present invention relates to the preparation method of molecular sieve catalyst.Especially, the present invention relates to from the method for the molecular sieve catalyst particle preparation molecular sieve catalyst of drying.
Background of invention
The microcellular structure that molecular sieve generally is made up of following material: belong to and be known as other crystal aluminosilicate of zeolites or crystallization aluminophosphates or crystalline silico-alumino-phosphate.Can be usually one or more as the organic amine of structure directing agent (directing agent) or quaternary ammonium salt in the presence of (this structure directing agent is also referred to as template), prepare molecular sieve from the reactant mixture that comprises following material by hydrothermal crystallization: the reaction source of the compound of siliceous and/or aluminium and/or phosphorus.
The composition that molecular sieve catalyst is made up of following material: be combined together to form molecular sieve particle greater than the particle of molecular sieve component.The molecular sieve catalyst particle also can comprise other component such as binding agent, and filler is like clay and optionally other catalytic activity agent such as rare-earth oxide, transition metal oxide or noble metal component.
The conventional method of preparation molecular sieve catalyst particle comprises following material is mixed: molecular sieve and binding agent, and other non-essential component such as filler and other catalyst component.Typically in solution, stir the mixture to form slurry and dry slurry to form the molecular sieve catalyst particle.After drying, the calcining particle is with sclerosis, and the activating catalyst particle.
For example WO99/21651 has described the method for preparing molecular sieve catalyst.This method comprises the step that molecular sieve and alumina sol are mixed, preparation alumina sol and remaining under the pH of 2-10 in solution.Spray-drying and calcining mixt then.The product of calcining is hard relatively, that is, wear-resistant according to reports.
US patent No.6153552 has described the another kind of method of preparation molecular sieve catalyst.Through mixing the preparation catalyst as the oxide containing silicon colloidal sol and the molecular screen material of binder material.Before spray-drying, regulate the pH of mixture.After spray-drying, the calcined catalyst material is to form the final catalyst product, and this product is hard relatively according to reports, that is, wear-resistant.
During the manufacturing of molecular sieve catalyst, can prepare catalyst particle, this particle has undesired performance such as undesired anti-wear performance or undesired granularity performance.Abandon such catalyst particle with it, make catalyst particle make again or circulate to provide user or manufacturer acceptable performance not as finding a kind of method, this method valuably.
Summary of the invention
The present invention provides the method for preparing the molecular sieve catalyst particle from the catalyst particle with some undesired performance.In fact, the present invention provides the manufacturing again or the circulation of molecular sieve catalyst or reprocesses to provide user or manufacturer acceptable performance.
In one embodiment, a kind of method for preparing the molecular sieve catalyst particle is provided, this method comprises:
A) the first dry molecular sieve catalyst is provided;
B) the first dry molecular sieve catalyst is combined to form water-carbon monoxide-olefin polymeric with water;
C) mixing water-carbon monoxide-olefin polymeric is to form slurry; With
D) dry slurry is to form the molecular sieve catalyst particle of second drying.
In another embodiment, the method for the molecular sieve catalyst particle that a kind of circulation has undesired performance is provided, this method comprises:
(i) mixing comprises molecular sieve, the composition of binding agent and water;
(ii) dry compsns is to form the molecular sieve catalyst of first drying;
At least a portion first dry molecular sieve catalyst is combined with water to form water-carbon monoxide-olefin polymeric;
(iv) mixing water-carbon monoxide-olefin polymeric is to form slurry; With
(v) dry slurry is to form the molecular sieve catalyst particle of second drying.
In another embodiment still; The method for preparing molecular sieve catalyst composition is provided; This method comprises: the molecular sieve catalyst particle that first drying is provided; Wherein when calcining, the first dry molecular sieve catalyst particle obtains containing greater than the calcining combination of molecular sieve of 5wt% average grain diameter more than or equal to 250 microns catalyst particle; Dry molecular sieve catalyst particle is combined with water to form slurry; With dry slurry to form molecular sieve catalyst composition.
In all embodiments of the present invention, the water that preferably combines with the first dry molecular sieve catalyst comprises at least 95wt% water and/or has no the molecular sieve particle basically.Preferably, before combine with the molecular sieve catalyst particle of drying water base under neutral pH.
The first dry molecular sieve catalyst can not calcined and therefore can comprise mould material.Preferably, mould material be selected from triethylamine, cyclohexylamine, piperidines, di-n-propylamine, pyridine, isopropylamine, tetraethyl ammonium salt, and composition thereof.
The molecular sieve catalyst of preferred mixing first drying and water are with the particle of the molecular sieve catalyst of broken first drying.
Form slurry, preferably this slurry viscosity of using Brookfield LV-DVE viscosimeter with No.3 rotating shaft under 10rpm, to measure is 100cP-9, and 000cP and solids content are 10wt%-75wt%.
Dry then slurry is to form the particle of the second dry molecular sieve catalyst.Preferred drying is through spray-drying.
Can the particle of the second dry molecular sieve catalyst be calcined.Preferably, at e) in the EMARI of the molecular sieve catalyst particle that obtains be not more than 1wt%/hr, preferably be not more than 0.7wt%/hr, most preferably be not more than 0.3wt%/hr, and/or have such granularity and make the diameter of 50% particle greater than 30 μ m with less than 150 μ m.
The first dry molecular sieve catalyst preferably includes silicoaluminophosphamolecular molecular sieve; More preferably be selected from following silicoaluminophosphamolecular molecular sieve: SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, its containing metal molecular sieve, and composition thereof, even more preferably be selected from following silicoaluminophosphamolecular molecular sieve: SAPO-18, SAPO-34, ALPO-34 and ALPO-18, its containing metal molecular sieve, and composition thereof.In another embodiment, the first dry molecular sieve catalyst be selected from have CHA, the silicoaluminophosphamolecular molecular sieve of framework types that AEI or CHA and AEI combine.
The first dry molecular sieve catalyst also can comprise and is selected from following binding agent: hydrated alumina, silica and/or other inorganic oxide sol and/or be selected from following filler: clay, clay type composition and composition thereof.
The present invention also relates to a kind of calcining molecular sieve catalyst composition that comprises catalyst particle, wherein after calcining, the EMARI of catalyst particle is equal to or less than 0.7wt%/hr, preferably less than 0.3wt%/hr.
Molecular sieve catalyst by the inventive method preparation is to transform the useful catalyst that the raw material that comprises at least a oxygenate becomes alkene.
Detailed Description Of The Invention
The present invention provides the method for preparing the molecular sieve catalyst particle.Accomplish this method through following mode: the first dry molecular sieve catalyst is combined with water forming water-carbon monoxide-olefin polymeric, from water-carbon monoxide-olefin polymeric formation slurry and dry slurry to produce the molecular sieve catalyst of second drying.This method provides drying or substantially dry especially, or the manufacturing again of the molecular sieve catalyst of part drying, and circulation or reprocessing (reworking) can be the catalyst particle that user or manufacturer accept to obtain performance.Usually after the molecular sieve catalyst of calcining drying, observe such performance.These performances comprise acceptable granularity, size distribution, particle density and particle hardness.
According to the present invention, the first dry molecular sieve catalyst is combined to form water-carbon monoxide-olefin polymeric with water.Combine with the first dry molecular sieve water base originally be pure water, promptly comprise 95wt% water at least, preferred 97wt% water at least, the most preferably water of 98wt% water at least.This water can optionally comprise less than 5wt%, preferably less than 3wt% be more preferably less than other compound of 2wt%.The non-limitative example of compound comprises alcohol, aldehyde, ester, ether, salt, soluble carbon hydrochlorate, oxide, hydroxide, acid, alkali, water-soluble polymer like this.Preferably, however water should comprise the least possible so other component.Under any circumstance, water base that combines with the first dry molecular sieve does not contain any molecular sieve particle, and promptly this water comprises the molecular sieve less than 1wt%.
In the combining of the first dry molecular sieve and water, addition sequence is not crucial.Can the first dry molecular sieve catalyst be added to the water, can water be joined in the first dry molecular sieve catalyst or the water and the first dry molecular sieve catalyst are combined.
Water-carbon monoxide-olefin polymeric comprises the particle and the water of the molecular sieve catalyst of first drying.Optionally, can other component be joined in water-carbon monoxide-olefin polymeric.Yet water-carbon monoxide-olefin polymeric does not comprise other molecular sieve beyond initial existence the in the first dry molecular sieve catalyst.Therefore method of the present invention is different from other catalyst circulation method, and wherein the molecular sieve catalyst particle with circulation mixes with the slurry that comprises other molecular sieve.In such method, the water-carbon monoxide-olefin polymeric that during round-robin method, forms comprises other molecular sieve, the molecular sieve that promptly in the recycling catalyst particle, does not exist at first.
The first dry molecular sieve catalyst is made up of the catalyst particle that comprises following material: be combined together to form the molecular sieve particle greater than the catalyst particle of individual molecule sieve particle.The molecular sieve catalyst particle also can comprise other component such as filler, for example clay and other catalytic activity agent, for example, metallic compound.
The performance that the first dry molecular sieve catalyst has makes it be inappropriate for its required purposes.The present invention provides and allows circulation, or the undesired like this molecular sieve catalyst of reprocessing has the method for recruit's sieve catalyst of desired properties with production.
For method of the present invention, the mixture that dry expression is used to form molecular sieve catalyst has experienced the heat in drying or the forming unit but has not been calcined.At least a portion liquid that uses during catalyst is made has been removed in dry also expression, and this manufacturing is also referred to as preparation.Method of the present invention can be used with molecular sieve catalyst composition, has removed the liquid that is used to make partly, basically or fully from this molecular sieve catalyst composition.
After such drying, molecular sieve can still be included in the structure directing molecule (template) that uses during molecular sieve is made.The drying of using does not in this manual comprise calcining.Calcining is burning process basically, and this burning process carries out under the temperature higher than drying process.Burning process at about 200 ℃-Yue 900 ℃, carries out under preferred about 250 ℃-Yue 850 ℃ and the more preferably from about 300 ℃-Yue 800 ℃ temperature preferably in the presence of oxygen-containing gas.
Can accept or unacceptable performance for confirming whether dry molecular sieve catalyst has, must calcine a part of molecular sieve catalyst usually to confirm one or more performances.If the catalyst of part calcining shows one or more undesired performances, with drying, but the remainder catalyst of calcining does not combine with water to form water-carbon monoxide-olefin polymeric.Mixing water-carbon monoxide-olefin polymeric is to form slurry.Dry then this slurry is to form so-called second catalyst particle.Can calcine the sample of this material and test required performance again.If reach required performance, then can calcine the remainder of the catalyst of second drying like needs.If still do not reach one or more performances, the iterative process step is up to reaching gratifying test result and as needing can to calcine then the remainder of dry catalyst.The present invention is therefore particularly useful to monitoring and optimization catalyst manufacturing process.
In embodiments of the invention, the first dry molecular sieve catalyst comprises mould material.Usually the mould material that is also referred to as structure directing agent is the compound that is used to prepare crystalline molecular sieve.During the formation of molecular sieve, form and be enclosed in mould material crystalline texture on every side basically.
Template can still exist in the carbon monoxide-olefin polymeric of first drying.It is finally removed from the carbon monoxide-olefin polymeric of second drying to form final catalyst composition product.Typically remove template through calcining or other chemical technology such as wash-out type process, it stays huge pore system in crystalline texture.This pore system is commonly called intracrystalline pore system.
The representative template that can be included in the first dry catalyst particle comprises tetraethyl ammonium salt, cyclopentamine, amino methyl cyclohexane, piperidines, triethylamine, cyclohexylamine, triethyl group aminoethyle alcohol, morpholine, di-n-propylamine (DPA), pyridine, isopropylamine and bond thereof.Preferred template be triethylamine, cyclohexylamine, piperidines, pyridine, isopropylamine, tetraethyl ammonium salt, di-n-propylamine, and composition thereof.The tetraethyl ammonium salt comprises tetraethyl ammonium hydroxide (TEAOH), phosphoric acid tetraethyl ammonium, fluoridizes tetraethyl ammonium, tetraethylammonium bromide, etamon chloride, acetate tetraethyl ammonium.
The first dry molecular sieve catalyst that is used to prepare catalyst of the present invention can comprise the molecular sieve component of any kind of.This component comprises zeolite or nonzeolite, preferred nonzeolite.In one embodiment, this molecular sieve be average cell size less than about 5 dusts, preferred average cell size is about 3-5 dust, more preferably the aperture non-zeolite molecular sieve of 3.5-4.2 dust.These cell sizes be contain 8 yuan of rings molecular sieve typical case have.
Conventional crystal silicon-aluminate zeolite with catalytic activity is the desired molecule sieve that can be used for preparing catalyst of the present invention.The example of zeolitic material is described in U.S. patent Nos.3660274 and 3944482 like this, and these two documents are hereby incorporated by.The non-limitative example that can be used for the zeolite of the present invention's enforcement comprises natural and synthetic zeolite.These zeolites are included in the structure type zeolite that is comprised in the following document: " Atlas of Zeolite Framework Types ", editor Ch.Baerlocher, W.M.Meier; D.H.Olson; The 5th correction, Elsevier, Amsterdam; 2001, the description of the document is hereby incorporated by.
Zeolite typically has at least about 2 silicon aluminium (SiO 2/ Al 2O 3) mol ratio and have the even bore dia of about 3-15 dust.They generally also comprise alkali metal cation, like sodium and/or potassium and/or alkaline earth metal cation, like magnesium and/or calcium.Be to increase the catalytic activity of zeolite, the alkali metal content that possibly need to reduce crystalline zeolite is to less than about 5wt%, preferably less than about 1wt% be more preferably less than about 0.5wt%.As known in the art, can (at this periodic table of elements of mentioning at Handbook of Chemistry and Physics, Chemical Rubber PublishingCompany publishes by the cationic exchange that is selected from periodic table of elements IIB-VIII family with one or more; Cleveland; The Ohio, the 45th edition, 1964 or the 73rd editions; Provide in 1992), and with the alkaline adduct of hydrogen ion or hydrogen ion (like NH 4 +, it can the time change into hydrogen ion in calcining) exchange alkali metal content is reduced.Required cation comprises rare-earth cation, calcium, magnesium, hydrogen and composition thereof.Ion-exchange process is well known in the art and is described in, for example, U.S. patent No.3140249, U.S. patent No.3142251 and U.S. patent No.1423353, therefore the instruction of the document is incorporated herein by reference.
The example that is applicable to zeolite of the present invention comprises large pore zeolite, mesopore zeolite and pore zeolite.The cell size of large pore zeolite is generally＞7 dusts and comprise zeolite type such as MAZ, MEI, FAU, EMT.The example of large pore zeolite comprises zeolite L, zeolite Y, zeolite Z, offretite, Ω, β, modenite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20.The cell size of middle cell size catalyst is generally＜7 dusts, and preferred about 5 dusts-6.8 dust and general hole hole are by about 10-12, and MFI, MEL, MTW, EUO, MTT, HEU, FER and TON are formed and comprised to preferred about 10 ring structures.The example of mesopore zeolite comprises ZSM-34, ZSM-38 and ZSM-48.The cell size of aperture degree zeolite is about 3 Ai-Yue 5.0 dusts.Generally speaking, the hole hole of this structure is by about 8-10, and CHA, ERI, KFI, LEV and LTA are formed and comprised to preferred about 8 ring structures.The example of pore zeolite comprises ZK-4, ZK-5, zeolite A, zeolite T, sodium chabazite, chinoptilolite, chabasie and erionite.Zeolite also can comprise gallium silicate and titan silicate.
Non-zeolite molecular sieve also can be included in the first dry molecular sieve catalyst particle that is used for preparing catalyst of the present invention.Preferred non-zeolite molecular sieve comprises the metal aluminophosphate molecular sieve.
On anhydrous basis, the metal aluminophosphate molecular sieve can be represented by following empirical formula:
mR:(M xAl yP z)O 2
Wherein R representes at least a template, preferred organic formwork agent, and m is every mole of (M xAl yP z) O 2R molal quantity and the numerical value of m be 0-1, preferred 0-0.5 and 0-0.3 most preferably; X; Y; Represent Al with z; P and M are as the mole fraction of tetrahedral oxide, and wherein M is the metal that is selected from periodic table of elements IA, IIA, IB, IIB, IVB, VB, VIB, VIIB, VIIIB and lanthanide series, and preferred M is selected from a kind of of Si, Ge, Co, Cr, Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn, Zr and composition thereof.In one embodiment, m is more than or equal to 0.2, and x, and y and z are more than or equal to 0.01.In another embodiment, m is about 1 greater than 0.1-, and x is about 0.25 greater than 0-, and y is that 0.4-0.5 and z are 0.25-0.5, and more preferably m is 0.15-0.7, and x is 0.01-0.2, and y is that 0.4-0.5 and z are 0.3-0.5.
The example of the metal aluminophosphates catalyst molecule sieve that can in the molecular sieve catalyst of first drying, exist is described in detail in many open source literatures; This open source literature for example comprises; U.S. patent No.4567029 (MeAPO; Wherein Me is Mg, Mn, Zn or Co), U.S. patent No.4440871 (SAPO), European patent application EP-A-0159624 (ELAPSO; Wherein El is As, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. patent No.4554143 (FeAPO), U.S. patent No.4822478,4683217,4744885 (FeAPSO), EP-A-0158975 and U.S. patent No.4935216 (ZnAPSO), EP-A-0161489 (CoAPSO), EP-A-0158976 (ELAPO; Wherein EL is Co, Fe, Mg, Mn, Ti or Zn), U.S. patent No.4310440 (AlPO4), EP-A-0158350 (SENAPSO), U.S. patent No.4973460 (LiAPSO), U.S. patent No.4789535 (LiAPO), U.S. patent No.4992250 (GeAPSO), U.S. patent No.4888167 (GeAPO), U.S. patent No.5057295 (BAPSO), U.S. patent No.4738837 (CrAPSO), U.S. patent Nos.4759919; With 4851106 (CrAPO), U.S. patent Nos.4758419; 4882038; 5434326 and 5478787 (MgAPSO), U.S. patent No.4554143 (FeAPO), U.S. patent No.4894213 (AsAPSO), U.S. patent No.4913888 (AsAPO), U.S. patent Nos.4686092; 4846956 and 4793833 (MnAPSO), U.S. patent Nos.5345011 and 6156931 (MnAPO), U.S. patent No.4737353 (BeAPSO), U.S. patent No.4940570 (BeAPO), U.S. patent Nos.4801309; 4684617 and 4880520 (TiAPSO), U.S. patent Nos.4500651; 4551236 and 4605492 (TiAPO), U.S. patent Nos.4824554; (QAPSO, wherein Q is skeleton oxide unit [QO for 4744970 (CoAPSO), U.S. patent No.4735806 (GaAPSO), EP-A-0293937 2]) and U.S. patent Nos.4567029,4686093,4781814,4793984,4801364,4853197,4917876,4952384,4956164,4956165,4973785,5241093,5493066 and 5675050, all these documents are incorporated herein by reference at this fully.
Other metal aluminophosphate molecular sieve is included in those (microporous crystalline metal phosphates of describing among the EP-0888187B1; SAPO4 (UIO-6)), the U.S. patent application series No.09/511943 (integrated hydrocarbon co-catalyst), disclosed PCT WO01/64340 on September 7 calendar year 2001 (molecular sieve of thoriated) and the R.Szostak that submit in U.S. patent No.6004898 (molecular sieve and alkaline-earth metal), on February 24th, 2000; Handbook of molecular sieves (Handbook of Molecular Sieves); VanNostrand Reinhold; New York, New York (1992), all these documents are incorporated herein by reference at this fully.
Most preferably, the molecular sieve that exists in the molecular sieve catalyst of first drying is that silicoaluminophosphate (SAPO) molecular sieve, aluminophosphate molecular sieve and metal thereof replace form.
The SAPO that can in the molecular sieve catalyst of the present invention's first drying, exist and the non-limitative example of ALPO molecular sieve comprise a kind of or bond of following material: SAPO-5; SAPO-8; SAPO-11; SAPO-16; SAPO-17; SAPO-18; SAPO-20; SAPO-31; SAPO-34; SAPO-35; SAPO-36; SAPO-37; SAPO-40; SAPO-41; SAPO-42; SAPO-44 (U.S. patent No.6162415); SAPO-47; SAPO-56; ALPO-5; ALPO-11; ALPO-18; ALPO-31; ALPO-34; ALPO-36; ALPO-37; ALPO-46; And metallic molecular sieve.Preferred molecular sieve comprises a kind of or bond of following material: SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34; Even a kind of or bond of more preferably following material: SAPO-18, SAPO-34, ALPO-34 and ALPO-18 and metallic molecular sieve thereof and most preferably a kind of or bond and the metallic molecular sieve thereof of SAPO-34 and ALPO-18.
At term mixture and the bond synonym and the composition of matter of thinking to contain two or more components of this use with the variation ratio, and no matter their physical state.Especially, it comprises the commensal of physical mixture and at least two kinds of different molecular sieve structures, for example those disclosed in the open No.WO98/15496 of PCT.In embodiments, molecular sieve is the coexisting material that in a molecular sieve is formed, contains two or more different crystalline texture phases.In another embodiment, molecular sieve comprises at least a coexisting phase of AEI and CHA framework types.For example, SAPO-18, ALPO-18 and RUW-18 have the AEI framework types and SAPO-34 has the CHA framework types.In further embodiment, molecular sieve comprises the mixture of coexisting material and non-coexisting material.
The first dry molecular sieve catalyst composition also can comprise binding agent.Can separately or combine the non-limitative example of the binding agent of existence to comprise various types of hydrated aluminas, silica and/or other inorganic oxide sol.A kind of preferred salic colloidal sol is aluminium chlorohydrate (aluminium chlorohydrate).Inorganic oxide sol plays adhesive, and it combines molecular sieve and other material that also can in carbon monoxide-olefin polymeric, exist, particularly after heat treatment like matrix or filler.When heating, inorganic oxide sol changes into the inorganic oxide matrix component.For example, alumina sol can change into alumina substrate after heat treatment.
Aluminium chlorohydrate is also referred to as the aluminium base colloidal sol of hydroxylating that comprises chlorine root gegenion of aluminium chloride hydrogel (aluminium chlorohydrol), has general formula Al mO n(OH) oCl pX (H 2O), wherein m is 1-20, and n is 1-8, and o is 5-40, and p is that 2-15 and x are 0-30.In one embodiment, binding agent is Al 13O 4(OH) 24Cl 712 (H 2O), as described in the following document: people such as G.M.Wolterman, Stud.Surf.Sci.and Catal.76, the 105-144 page or leaf, Elsevier, Amsterdam, 1993, the document is hereby incorporated by.In another embodiment; Other alumina material with the representative of following non-limitative example of one or more binding agents and one or more combines to exist: for example aluminum oxyhydroxide, gama-alumina, boehmite and transitional alumina such as Alpha-alumina, beta-alumina, gama-alumina, δ-aluminium oxide, ε-aluminium oxide, k-aluminium oxide, p-aluminium oxide, aluminium hydroxide, as gibbsite, bayerite, promise gibbsite, doyelite, and composition thereof.
In another embodiment, binding agent is an alumina sol, mainly comprises aluminium oxide, optionally comprises some silicon.In another embodiment still, binding agent is the peptization aluminium oxide that is prepared by following mode: adopt acid, preferably do not comprise the acid treatment hydrated alumina such as the pseudobochmite of halogen, with preparation colloidal sol or aluminium ion solution.The non-limitative example of commercially available colloidal alumina colloidal sol comprises the Co. available from Nalco Chemical, Naperville, the Nalco8676 of Illinois and available from Nyacol Nano Technology Inc., Boston, the Nyacol of Massachusetts.
The first dry molecular sieve also can comprise one or more matrixes or filler material.Matrix material is being effective aspect the total body catalyst cost of reduction usually; It assists the hot cave (thermal sink) of shielding from the heat of carbon monoxide-olefin polymeric as for example regeneration period; Densified carbon monoxide-olefin polymeric; Increase the conversion ratio in catalyst strength such as crushing strength and wearability and the control special process.
The non-limitative example of matrix material comprises one or more following materials: rare earth metal, comprise titanium dioxide, zirconia, magnesia, thorium oxide, beryllium oxide, quartz, silica or colloidal sol metal oxide, and composition thereof, for example silica-magnesia, silica-zirconia, silica-titania, silica-alumina and silica-alumina-thorium oxide.In embodiments, matrix material is a natural clay as from those of imvite and kaolin group.These natural claies comprise and being known as, for example, and the kaolin of Dixie, McNamee, Georgia and Florida clay.The non-limitative example of other matrix material comprises: galapectite, kaolinite, dickite, nacrite or anauxite.In one embodiment, with matrix material, preferred any clay experienced known modified technique such as calcining and/or acid treatment and/or chemical treatment before being used for catalyst preparation technology.
In a preferred embodiment, matrix material is clay or clay type composition, preferably have clay or the clay type composition of low iron or content of titanium dioxide and most preferably matrix material be kaolin.Have been found that but kaolin can form pumping, highly filled slurry, it is long-pending that it has low unsalted surface, and it is packed in together easily owing to its platelet structure.Matrix material, most preferably kaolinic preferable range particle mean size are about 0.6 μ m and the d of about 0.1 μ m- 90Size distribution is less than about 1 μ m.
Typically prepare the first dry molecular sieve catalyst composition by following mode: mixed molecular sieve, binding agent and matrix material are forming slurry in the presence of liquid, and dry slurry is to form the molecular sieve catalyst particle of first drying.
The binding agent quantity that is used to prepare the first dry molecular sieve catalyst typically is the about 30wt% of about 2wt%-; The preferred about 20wt% of about 5wt%-; The about 17wt% of 7wt%-more preferably from about is based on binding agent, molecular sieve and the matrix material gross weight of getting rid of liquid (after calcining).
In another embodiment, being used for binding agent that the first dry molecular sieve catalyst composition forms is 0 to the weight ratio of matrix material: 1-1: 1, preferred 1: 15-1: 2, more preferably 1: 10-1: 2 and most preferably 1: 6-1: 1.
The liquid that is used to form the molecular sieve catalyst of first drying can be known any liquid in the preparation catalyst field.The non-limitative example of suitable liquid comprises a kind of or bond of following material: water, alcohol, ketone, aldehyde and/or ester.Most preferred liquid is water.
Molecular sieve and matrix material and the non-essential binding agent that is used to prepare the first dry carbon monoxide-olefin polymeric can combine in identical or different liquid and can adopt any order, together, and simultaneously, in order, or its combination and combining.In preferred embodiments, use identical liquid, preferred water.
In one embodiment; Mix or the slurry of the mill molecular sieve, binding agent and the matrix material that are used to prepare the first dry carbon monoxide-olefin polymeric; To obtain the even slurry of molecular sieve catalyst composition subparticle, then this slurry is joined in the forming unit of the molecular sieve catalyst composition of producing first drying.This forming unit can be any known unit, like spray dryer, comminutor, extruder etc.In preferred embodiments, this forming unit is a spray dryer.Typically, this forming unit remains on is enough to remove under the temperature of most liquid from slurry.
When being shaped (or dry) unit when spray dryer is used as; Typically, adopt 150 ℃-550 ℃ average inlet temperature and 100 ℃-Yue 250 ℃ combination outlet temperature; The slurry of molecular sieve and matrix material and non-essential binding agent is joined in the spray-drying volume jointly.
During spray-drying, through nozzle, the distribution slurry becomes droplet with slurry, and similar aerosol spray gets into drying chamber.Adopt the pressure of 100psia-1000psia (690kPaa-6895kPaa) to fall, slurry is reached atomizing through single nozzle or a plurality of nozzle.In another embodiment, slurry is added through single nozzle or a plurality of nozzle with atomizing fluids such as air, steam, flue gas or any other suitable gas jointly.
In another embodiment still; Above-described slurry is guided into the edge of swiveling wheel; This swiveling wheel is scattered in droplet with slurry; Small drop sizes is controlled by many factors, and this factor comprises the speed of rotation of slurry viscosity, surface tension, flow, pressure and slurry temp, its shape of nozzle and size or wheel.Then the air through spray dryer and stream or adverse current in dry these drops to form the molecular sieve catalyst composition of part, basic or bone dry.
The example that can be used for preparing the drying process with atomizing of the first dry molecular sieve catalyst composition is disclosed among the U.S. patent No.4946814, is incorporated herein the description of the document.
In addition, except that molecular sieve, the first dry molecular sieve catalyst composition that is used for the inventive method can comprise one or more other catalytically-active materials.The result is that these other catalytically-active materials are introduced as the part of the carbon monoxide-olefin polymeric of first drying.
According to the present invention, the first dry molecular sieve catalyst is combined with water to mix said composition to form slurry to form water-carbon monoxide-olefin polymeric.Preferably, this mixing is enough to break and joins the more macroparticle in the solution.Generally speaking, it is strong to mix Shaoxing opera, and the particle that forms in the slurry is more little.Preferably use the mixing of high shear mixer.Generally speaking, these are the blenders that can rotate under at least about 3000rpm laboratory scale coordinate speed.
Can evaluate the granularity of slurry through the viscosity of measuring slurry indirectly.Generally speaking, viscosity is high more, and the granularity in the slurry is more little.The viscosity of slurry should too high feasible mixing not be effectively or not should too low feasible drying can not produce acceptable particle formation to broken macroparticle.In one embodiment of the invention, the viscosity of slurry is about 100cP (0.1Pa/sec)-Yue 9, and 500cP (9.5Pa/sec) uses the Brookfield LV-DVE viscosimeter with No.3 rotating shaft under 10rpm, to measure viscosity.The viscosity of preferred slurries is about 200cP (0.2Pa/sec)-Yue 8; 500cP (8.5Pa/sec); More preferably from about 350cP (0.375Pa/sec)-Yue 8, and 000cP (8Pa/sec) uses the Brookfield LV-DVE viscosimeter with No.3 rotating shaft under 10rpm, to measure viscosity.
In another embodiment, the solids content of slurry is the about 75wt% of about 10wt%-.The solids content of preferred slurries is the about 70wt% of about 15wt%-, and the about 65wt% of 20wt%-more preferably from about is based on the gross weight of slurry.Can use any conventional measure measure solid content.Yet, preferred especially CEM MAS 700 microwave Muffle furnaces with obtain with in the consistent result of the numerical value of this explanation.
Like needs, can be before the blend step or during regulate the pH of slurry.
Can use the dry slurry of any conventional drying method to form the molecular sieve catalyst composition of second drying.All methods of the molecular sieve catalyst composition of preparation first drying of in this file, early describing are suitable for producing the molecular sieve catalyst composition of second drying equally.
In one embodiment, the molecular sieve catalyst composition of calcining second drying.The molecular sieve catalyst composition of further sclerosis of calcining and/or activation second drying.Conventional calcination environment is the air that typically comprises a small amount of steam.Typical calcining heat is about 400 ℃-Yue 1,000 ℃, preferred about 500 ℃-Yue 800 ℃ and most preferably from about 550 ℃-Yue 700 ℃, and preferably in calcination environment such as air, nitrogen, helium, flue gas (combustion product of oxygen poor) or its any bond.
In one embodiment, the calcining of the molecular sieve catalyst composition of in many known device, preparing, this equipment comprises rotation calcining furnace, fluidized bed calcination stove, baking oven etc. intermittently.Calcination time typically depends on the hardenability and the temperature of molecular sieve catalyst composition.
In preferred embodiments, in nitrogen, under about 600 ℃-Yue 700 ℃ temperature, heat molecular sieve catalyst composition.Heating was carried out 30 minutes-15 hours usually, and preferred 1 hour-Yue 10 hours, more preferably from about 1 hour-Yue 5 hours and most preferably from about 2 hours-Yue 4 hours time.
Other method of activated molecular sieve carbon monoxide-olefin polymeric is described in; For example; U.S. patent No.5185310 (molecular sieve and the water to 450 of heating gel alumina ℃), disclosed PCT WO00/75072 on December 14th, 2000 (heating to stay the quantity of template), all documents are incorporated herein by reference at this fully.
Method of the present invention provides the method for producing molecular sieve catalyst composition, and said composition comprises to have makes them be suitable for the particle of the performance of catalysis use.They can be used for, for example, and dry gas and liquid; Be used for selectivity molecular separation based on size and polar behavior; As ion-exchanger; As hydrocarbon cracking, hydrocracking, disproportionation, alkylation, isomerization, oxidation and the oxygenate catalyst in the conversion of hydrocarbon; As chemistry carrier; Be used for gas-chromatography and be used for petroleum industry to remove normal paraffin hydrocarbons from distillate.More particularly, molecular sieve catalyst of the present invention is suitable for the catalyst that transforms to hydrocarbon as oxygenate.
In the embodiment of hoping most, the molecular sieve catalyst composition that is prepared by the inventive method can be used as the catalyst that oxygenate transforms to hydrocarbon.Therefore, the present invention also comprises the method through making following material contact produce light olefin: comprise the raw material of at least a oxygenate and the combination of molecular sieve of the dry or calcining that is prepared by the inventive method.
In this embodiment; Effectively producing under the process conditions of light olefin, promptly with the relevant effective temperature of production light olefin, pressure; WHSV (weight hourly space velocity) and; Optionally, under the effective dose diluent, the raw material that comprises oxygenate is contacted with molecular sieve catalyst composition.Below describe these conditions in detail.Usually, when oxygenate is in vapor phase, the oxygenate charging is contacted with catalyst.Perhaps, can or mix in the gas phase and liquid phase and carry out this technology in liquid phase.When in liquid phase or mixing gas phase and liquid phase, carrying out this technology, depend on catalyst and reaction condition, can obtain former different conversion ratios and the selectivity of expecting product.Term reactor in this use not only comprises the commercial size reactor and comprises pilot scale size reactors unit and laboratory mould examination reactor unit.
Generally can in wide temperature range, produce alkene.Effectively operating temperature range can be about 200 ℃-700 ℃.In the lower end of temperature range, the formation of required olefin product can significantly become significantly slowly.In the upper end of temperature range, this technology can not form the product of optimal number.Need about 300 ℃-500 ℃ operating temperature.
Can in any system of dynamic bed system or various Transport Bed rather than in fixed bed system, carry out this technology.Need under high-speed and in fluidized system, operate this reaction process especially.
Can in various extensive catalytic reactors, be used to produce the conversion of the oxygenate of light olefin; This reactor include, but not limited to fluidized-bed reactor and as at fluidisation engineering (Fluidization Engineering); D.Kunii and O.Levenspiel; Robert E.Krieger Publishing Co. New York, describe in 1977 and flow the tedge reactor, the document is incorporated herein by reference at this in full.In addition, adverse current free-falling reactor can be used in this conversion process.Referring to, for example, US-A-4068136 and fluidisation and fluid particles system (Fluidizationand Fluid-Particle Systems); The 48-59 page or leaf; F.A.Zenz and D.E.Othmo, Reinhold Publishing Corp., New York; 1960, being described in this and clearly being incorporated herein by reference of the document.
Can use any normal business scale reaction device system, this reactor assembly comprises fixed bed or moving bed system.Can be at 1hr -1～1000hr -1The following operation commercial size reactor assembly of weight hourly space velocity (WHSV).Under the situation of commercial size reactor, WHSV is defined as the hydrocarbon weight molecular sieve content weight of every catalyst per hour in the raw material.The hydrocarbon content is oxygenate and any hydrocarbon that can optionally combine with oxygenate.Hope that the molecular sieve content only representes to be included in the molecular sieve part in the catalyst.This has got rid of like binding agent, diluent, inert substance, the component of rare earth component etc.
Pressure also can change in wide region, comprises self pressure.Required pressure is the about 5MPa of about 0.5kPa-.The dividing potential drop of above-mentioned pressure representative oxygenate compound and/or its mixture.
For example, the quantity that one or more inert diluents can 1mol%-99mol% exists in raw material, based on all chargings that join reaction zone (or catalyst) and the total mole number of thinner composition.Typical diluent comprises, but must not be limited to helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, hydrogen, water, alkane, alkane (particularly methane, ethane and propane), alkylidene thing (alkylenes), aromatic compounds, and composition thereof.Required diluent is water and nitrogen.Water can adopt liquid or the steam form is injected.
Can adopt intermittently, semicontinuous or continuation mode carries out this technology.Can in many reaction zones of single reaction district or serial or parallel connection layout, carry out this technology.
The level of conversion that can keep oxygenate is to reduce the level of not hoping accessory substance.Also can keep the needs of sufficiently high conversion ratio with the commercial undesired level of avoiding unreacting material circulation.When conversion ratio moves to 98mol% or more hour from 100mol%, seen the reduction of not hoping accessory substance.It is commercial acceptable being circulated to many about 50mol% chargings.Therefore, the transform level that reaches two purposes is about 98mol% of about 50mol%-and required ground, the about 98mol% of about 85mol%-.Yet also acceptable is to reach the conversion ratio of 98mol%-100mol% to simplify circulation technology.The many methods that can use those skilled in the art to be familiar with remain on the oxygenate conversion rate under this level.Example comprises, but must not be limited to, and regulates one or more of following factor: reaction temperature, pressure; Flow rate (being WHSV), the level of catalyst regeneration and degree, the quantity of catalyst recycle; The particular reactor configuration, feed composition and influence the other factors of conversion ratio.
If require regeneration, can molecular sieve catalyst be introduced the renewing zone continuously as moving bed, wherein it can be regenerated, for example through removing carbonaceous material or passing through the oxidation in oxygen-containing atmosphere.In required embodiment,, make catalyst experience regeneration step through the carbon-containing sediment that accumulates during the conversion reaction of burnouting.
The oxygenate raw material comprises at least a organic compound that comprises at least one oxygen atom, like aliphatic alcohol, ether, carbonyls (aldehyde, ketone, carboxylic acid, carbonic ester, ester etc.).When oxygenate was alcohol, this alcohol can comprise and contain 1-10 carbon atom, more preferably the aliphatic part of 1-4 carbon atom.Representative alcohols comprises but must not be limited to lower straight and branched aliphatic alcohol and their unsaturated counter pair.The example of suitable oxygenate compound includes, but are not limited to: methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, C 4-C 20Alcohol, ethyl methyl ether, dimethyl ether, diethyl ether, Di Iso Propyl Ether, formaldehyde, dimethyl carbonate, dimethyl ketone, acetate, and composition thereof.Required oxygenate compound is methyl alcohol, dimethyl ether or its mixture.
The method for preparing required olefin product in the present invention can comprise from the other step of hydrocarbon such as oil, coal, Tar sands, shale, living beings and these oxygenate of natural gas preparation.The preparation method for compositions is known in the art.These methods comprise the fermentation of alcohol or ether, preparation synthesis gas, transform synthetic pneumatolytic alcohol or ether then.Can produce synthesis gas by known method such as steam reformation, self-heating recapitalization and partial oxidation.
Can polymerization by the alkene of Catalyst Production of the present invention to form polyolefin, particularly polyethylene and polypropylene.Can use from alkene and form polyolefinic conventional method.Need catalysis process.Need metallocene, Ziegler/Natta and acid catalysis system especially.Referring to, for example, U.S. patent Nos.3258455,3305538,3364190,5892079,4659685,4076698,3645992,4302565 and 4243691, the catalyst of every piece of document and technology are described in this and clearly are incorporated herein by reference.Generally speaking, these methods are included under the temperature and pressure of effective formation polyolefin product, make olefin product and polyolefin form catalyst and contact.
It is metalloscene catalyst that required polyolefin forms catalyst.Required operating temperature be 50 ℃-240 ℃ with reaction can low, in or carry out under the high pressure, this pressure under any circumstance be that about 1 crust-200 clings to.For the technology of in solution, carrying out, can use inert diluent and required operating pressure is 10 crust-150 crust, and required temperature range is 120 ℃-230 ℃.For gas phase process, needing temperature to be generally 60 ℃-160 ℃ and operating pressure is 5 crust-50 crust.
Except that polyolefin, can form many other alkene derivatives from the alkene of producing by the present invention.These materials comprise; But be not limited to the tripolymer and the dimer of aldehyde, alcohol, acetate, linear alpha olefin, vinylacetate, ethylene dichloride and vinyl chloride, ethylbenzene, oxirane, cumene, isopropyl alcohol, methacrylaldehyde, allyl chloride, expoxy propane, acrylic acid, ethylene-propylene rubber and acrylonitrile and ethene, propylene or butylene.
In the catalysis process that uses molecular sieve catalyst composition produced according to the invention, catalyst particle must satisfy some particle requirement, and this requirement comprises granularity, size distribution, particle density and particle hardness.Be used for proving that the example in the useful molecular sieve catalyst particle performance of Catalytic processes comprises following non-limitative example.
After calcining; The particle of the molecular sieve catalyst of second drying can have such size distribution; Make the average diameter that is not more than about 10wt% catalyst particle be less than or equal to 20 μ m; The average diameter that preferably is not more than about 5wt% catalyst particle is less than or equal to 20 μ m and is less than or equal to 20 μ m more preferably no more than the average diameter of about 2wt% catalyst particle.In another embodiment; Carbon monoxide-olefin polymeric is made up of catalyst particle; Wherein after the calcining of carbon monoxide-olefin polymeric; The average diameter that is not more than about 10wt% catalyst particle is more than or equal to about 250 μ m, and the average diameter that preferably is not more than about 5wt% catalyst particle is more than or equal to about 250 μ m, more preferably no more than the average diameter of about 2wt% catalyst particle more than or equal to about 250 μ m.
In another embodiment of the invention, the granularity of the catalyst particle of calcining prepared according to the methods of the invention makes carbon monoxide-olefin polymeric be specially adapted to the fluidized-bed reaction system.In one embodiment, the catalyst of calcining is 2＜d with the distribution of particles of μ m 10＜50,30＜d 50＜120 and 50＜d 90＜250, d wherein 10Be that wherein the sample cumulative volume reaches the average diameter of total amount 10%, d 50Be that wherein the sample cumulative volume reaches the average diameter of total amount 50% and d 90Be that wherein the sample cumulative volume reaches the average diameter of total amount 90%.The catalyst of preferred calcining is 5＜d with the distribution of particles of μ m 10＜45,40＜d 50＜100 and 70＜d 90＜200, more preferably the distribution of particles with μ m is 10＜d 10＜40,50＜d 50＜100 and 90＜d 90＜150.
In another embodiment of the invention, comprise the particle of highly abrasion-resistant from the carbon monoxide-olefin polymeric of the inventive method preparation.Such particle is specially adapted to the fluidisation catalysis system.
In the present invention, use ExxonMobil wear rate index (EMARI) to measure wearability, or catalyst hardness.Since many other methods be not enough to measure unusual highly abrasion-resistant molecular sieve catalyst such as prepared in accordance with the present invention those, therefore be superior to other measuring method and use EMARI.
The EMARI method is similar to conventional Davison index method.EMARI is more little, and catalyst is wear-resisting more, and is therefore hard more.Through adding 6.0 ± 0.1g granularity is that the catalyst of 53-125 micron is measured EMARI in hardened steel abrasion cup.With about 23,700scc/min nitrogen through moisture bubbler bubbling with moistening nitrogen.Wet nitrogen leaves abrasion equipment through the abrasion cup with through the porous fibre sleeve pipe.Flowing nitrogen is removed thinner particle, and bigger particle remains in the cup.The porous fibre sleeve pipe separates thin catalyst particle from the nitrogen that leaves through sleeve pipe.The fine particle that is retained in the sleeve pipe is represented through the broken catalyst of abrasion.
Keep flowing 1 hour through the nitrogen of abrasion cup.Take out the particulate of collecting the sleeve pipe from this unit.New casing is installed then.Under same gas stream and moisture level, other 3 hours of the catalyst that stays in the abrasion wear unit.The particulate of collecting in the recovery of casing.Weigh after the first hour thin catalyst particle of the separation of collecting by sleeve pipe.What on basis per hour, represent is EMARI in gram fine particle quantity divided by the catalyst initial quantity that joins in the abrasion cup, in wt%/hr.
EMARI＝C/(B+C)/D×100％
Wherein
The catalyst weight that B=stays in the cup after wear test
The thin catalyst particle weight that C=collects after abrasion are handled first hour
D=after abrasion in first hour are handled in hour the processing duration
Be not more than about 1wt%/hr from the EMARI of the calcining molecular sieve catalyst particle of the inventive method preparation requiredly.The EMARI of preferred calcining molecular sieve catalyst particle is not more than about 0.7wt%/hr, more preferably no more than about 0.3wt%/hr.
Therefore the present invention also comprises the molecular catalyst of calcining, and this catalyst comprises that EMARI is not more than about 1wt%/hr, preferably is not more than about 0.7wt%/hr, more preferably no more than the catalyst particle of about 0.3wt%/hr.
Understand the present invention better with reference to following examples, this embodiment is used for explaining the specific embodiments like the overall range of the present invention that requires.
Embodiment 1
According to the dry molecular sieve catalyst composition A1 of following process preparation, A2, A3 (molecular sieve catalyst composition that first in the context of the present invention is dry):
Through water and solid composite are mixed the preparation slurry; This solid composite comprises 40wt%SAPO-34, and 10.6wt% is derived from aluminium oxide (ReheisChemicals Inc., the Berkley Heights of aluminium chlorohydrate; NJ); With the 49.4wt% kaolin clay (Engelhard Corporation, Gordon, CA).This slurry is made up of the 45wt% solid composite.Then in spray dryer dry slurry to obtain the first dry molecular sieve catalyst composition A1, A2, and A3.
Embodiment 2
The molecular sieve catalyst composition of the every kind of drying that from embodiment 1, is prepared by following mode prepares slurry: add every kind first dry molecular sieve catalyst composition of a part in the deionized water to form the composition that comprises the 45wt% solid.The initial scraper that uses stirs composition.(Yamato Scientific AmericaInc., Orangeburg NY) mixed 5 minutes under 600rpm, under 2400rpm, mixed 5 minutes then then composition to be used Yamato DL-2100 blender.
From carbon monoxide-olefin polymeric A1, A2 is called slurry 1 respectively below the slurry that A3 obtains, slurry 2 and slurry 3 in this way.
Embodiment 3
Use Silverson SR4 high-shear mixer (Silverson Machines, Inc., Massachusetts) under 6500rpm, a part of slurry 1 and slurry 2 further to be mixed 3 minutes.Be called slurry HS1 and slurry HS2 respectively below the slurry that adopts high shear mixing to obtain.
Embodiment 4
Relatively at the slurry 1 of embodiment 2 preparations with in the viscosity of the slurry HS1 of embodiment 3 preparations.The Brookfield LV-DVE viscosimeter that use has a No.3 rotating shaft is measured the viscosity of every kind of slurry under various rpm.The result sees table 1.
The slurry viscosity
Figure G02827245519960505D000201
of table 1-reprocessing
Data indication in the table 1 uses the slurry of high shear mixing preparation to have higher viscosity.This is the indication of following situation: viscosity is high more, and the granularity of solid is more little in the slurry.
Embodiment 5
With a part of sample A1 of preparation among the embodiment 1, A2 and A3 calcined 2 hours in air under 650 ℃ in Muffle furnace.This obtains sample A1calc respectively, A2calc and A3calc.The wearability of these samples of EMARI measurements determination of describing in the operation instructions.The result sees table 2.
Embodiment 6
Use a part of slurry 2 and slurry 3 of preparation among the Yamato DL-41 spray dryer spray-drying embodiment 2, this spray dryer is being pressed the operation of spray pattern use 1mm atomizer.The spray-drying condition is: the 40g/min feed rate, and 350 ℃ of inlet temperatures, 1 crust atomizing pressure, 60% airflow carrier is set.This obtains the combination of molecular sieve B2 and the B3 of second drying respectively.
Spray-dired product is collected in cyclone separator and in Muffle furnace, under 650 ℃, in air, calcined 2 hours.This obtains sample B2calc and B3calc respectively.The wearability of these samples of EMARI measurements determination of describing in the operation instructions.The result sees table 2.
Embodiment 7
Use a part of slurry HSI and the slurry HS2 of preparation among the Yamato DL-41 spray dryer spray-drying embodiment 3, this spray dryer is pressed spray pattern and is used the operation of 1mm atomizer.The spray-drying condition is: the 40g/min feed rate, and 350 ℃ of inlet temperatures, 1 crust atomizing pressure, 60% airflow carrier is set.This obtains the combination of molecular sieve C1 and the C2 of second drying respectively.Spray-dired product is collected in cyclone separator and in Muffle furnace, under 650 ℃, in air, calcined 2 hours.This obtains sample C1calc and C2calc respectively.The wearability of these samples of EMARI measurements determination of describing in the operation instructions.The result sees table 2.
The EMARI (wt%/hr)
Figure G02827245519960505D000211
of the molecular sieve catalyst of table 2-calcining
EMARI is low more, and material is hard more, or wearability is big more.
Embodiment 8
(Microtrac Inc., Clearwater FL.) analyze the sample B2calc for preparing among the embodiment 6 and 7, B3calc, the size distribution of C1calc and C2calc to use Microtrac S3000 laser scanning Particle Size Analyzer.Data are seen table 3.
Size distribution
Figure G02827245519960505D000221
in the molecular sieve catalyst of table 3-calcining
Think that all samples shown in the table 3 is the material from the calcining of the inventive method preparation.Data in the table 3 show to be compared with B3calc with sample B2calc, and the material (C1calc and C2calc) for preparing from the high shear mixing slurry has less macroparticle after calcining.

Claims (24)

1. method for preparing the molecular sieve catalyst particle comprises:
A) the first dry molecular sieve catalyst is provided, this first dry molecular sieve catalyst is made up of the catalyst particle that comprises following material: be combined together to form the molecular sieve particle that sieves the catalyst particle of particle greater than individual molecule; Wherein the performance that has of this first dry molecular sieve catalyst makes it be inappropriate for required purposes;
B) the first dry molecular sieve catalyst is combined to form water-carbon monoxide-olefin polymeric with water, this water-carbon monoxide-olefin polymeric does not comprise other molecular sieve beyond the molecular sieve that exists at first in the molecular sieve catalyst of first drying;
C) mixing water-carbon monoxide-olefin polymeric is to form slurry; With
D) dry this slurry is to form the molecular sieve catalyst particle of second drying.
2. the process of claim 1 wherein that the first dry molecular sieve catalyst comprises mould material.
3. the method for claim 2, wherein template be selected from triethylamine, cyclohexylamine, piperidines, di-n-propylamine, pyridine, isopropylamine, tetraethyl ammonium salt, and composition thereof.
4. the process of claim 1 wherein that mixing water-carbon monoxide-olefin polymeric makes at c) in the slurry that obtains comprise particle less than the particle that comprises in the first dry combination of molecular sieve.
5. the arbitrary method of aforementioned claim further comprises e) calcine the particle of this second dry molecular sieve catalyst.
6. the method for claim 5, wherein after calcining, the particle of the second dry molecular sieve catalyst has such size distribution, makes the average grain diameter that is not more than the 10wt% particle be less than or equal to 20 μ m.
7. the method for claim 5, wherein after calcining, the particle of the second dry molecular sieve catalyst has such size distribution, makes the average grain diameter that is not more than the 10wt% particle be equal to or greater than 250 μ m.
8. the method for claim 7 is wherein carried out down combining of the first dry molecular sieve catalyst and water mixing, and makes the molecular sieve catalyst particle fragmentation of at least a portion first drying.
9. the process of claim 1 wherein and is combining before water base with the first dry molecular sieve catalyst under neutral pH.
10. the process of claim 1 wherein that the slurry viscosity of using Brookfield LV-DVE viscosimeter with No.3 rotating shaft under 10rpm, to measure is 100cP-9,000cP.
11. the process of claim 1 wherein at c) in the solids content of slurry of preparation be 10wt%-75wt%.
12. the method for claim 5 is wherein at e) in the EMARI of the molecular sieve catalyst particle that obtains be not more than 1wt%/hr.
13. the method for claim 12 is wherein at e) in the EMARI of the molecular sieve catalyst particle that obtains be not more than 0.7wt%/hr.
14. the method for claim 13 is wherein at e) in the EMARI of the molecular sieve catalyst particle that obtains be not more than 0.3wt%/hr.
15. the method for claim 5 is wherein at e) in the granularity of the molecular sieve catalyst particle that obtains make the diameter of 50% particle greater than 30 μ m with less than 150 μ m.
16. the process of claim 1 wherein dry d by spray-drying) in slurry.
17. the process of claim 1 wherein that the first dry molecular sieve catalyst comprises silicoaluminophosphamolecular molecular sieve.
18. the method for claim 17, wherein silicoaluminophosphamolecular molecular sieve be selected from SAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, its containing metal molecular sieve, and composition thereof.
19. the method for claim 18, wherein silicoaluminophosphamolecular molecular sieve be selected from SAPO-18, SAPO-34, ALPO-34 and ALPO-18, its containing metal molecular sieve, and composition thereof.
20. the method for claim 19, wherein silicoaluminophosphamolecular molecular sieve be selected from have CHA, the silicoaluminophosphamolecular molecular sieve of framework types that AEI or CHA and AEI combine.
21. the process of claim 1 wherein that the first dry molecular sieve catalyst comprises is selected from following binding agent: hydrated alumina, silica and other inorganic oxide sol.
22. the process of claim 1 wherein that the first dry molecular sieve catalyst comprises the binding agent that is selected from aluminium chlorohydrate.
23. the process of claim 1 wherein that the first dry molecular sieve catalyst is included as the filler of clay.
24. a circulation has the method for the molecular sieve catalyst particle of undesired performance, comprising:
(i) mixing comprises molecular sieve, the composition of binding agent and water;
(ii) dry said composition is to form the molecular sieve catalyst of first drying, and this first dry molecular sieve catalyst is made up of the catalyst particle that comprises following material: be combined together to form the molecular sieve particle greater than the catalyst particle of individual molecule sieve particle;
(iii) adopt the molecular sieve of (ii) middle first drying that obtains of the arbitrary method treatment step of claim 1-23.
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